Cationic alkoxyamines and their use in producing nano particles from natural or synthetic clays

ABSTRACT

The instant invention relates to cationic alkoxyamines, which are useful as polymerization initiators/regulators in a controlled stable free radical polymerization process to produce intercalated and/or exfoliated nanoparticles from natural or synthetic clays. The invention also relates to improved nanocomposites produced by this process and to the use of these nanocomposite compositions as, for example, coatings, sealants, caulks, adhesives and as plastic additives.

The instant invention relates to cationic alkoxyamines, which are usefulas polymerization initiators/regulators in a controlled free radicalpolymerization process to produce intercalated and/or exfoliatednanoparticles from natural or synthetic clays. The invention alsorelates to improved nanocomposite compositions produced by this processand to the use of these nanocomposite compositions as, for example,coatings, sealants, caulks, adhesives and as plastic additives.

One way of improving polymer properties is by adding a natural orsynthetic clay material to polymers to form composite materials.However, incorporating clays into polymers may not provide a desirableimprovement in the physical properties, particularly mechanical andoptical properties of the polymer may be adversely affected.

Nanonocomposite compositions containing finely dispersed natural orsynthetic clay with at least partially intercalated and/or exfoliatedlayers and mixtures of ethylenically unsaturated monomers and/orpolymers therefrom have therefore attracted much interest in the lastyears. These materials combine the desired effects of dispersed clay byavoiding the negative influence on, for example, the mechanical oroptical properties.

Such compositions, methods for making them and their use in polymers andcoatings are for example described in WO 02/24759. Polymerizationprocesses are described using montmorillonite clay, acrylate monomersand for example ammonium persulfate as radical initiator. Thisconventional polymerization process leads to polymers with broadmolecular weight distributions and a high polydispersity index (PD).

Y. Sogah et al., J. Am. Chem. Soc. 1999, 121, 1615-1616 describe thesynthesis of dispersed nanocomposite compositions by in situ living freeradical polymerization of styrene using a silicate-anchored initiator.The nitroxyl compound used is a 2,2,6,6 tetramethyl-piperidinealkoxyamine. Although Sogah et al. have shown the principal possibilityof preparing nanocomposite compositions by controlled free radicalpolymerization, they have been limited to styrene, since the knowninitiators/regulators are not efficient enough to polymerize acrylatesor methacrylates with reasonable conversion rates at acceptabletemperatures.

The present invention provides alkoxyamines, which can be anchored tonatural or synthetic clays by a cationic anchor group and which have ahigh reactivity towards acrylates, methacrylates, styrene and othermonomers resulting in a controlled molecular weight with narrowmolecular weight distribution. With these compounds polymerization leadsto high monomer to polymer conversions in short times and at relativelylow temperatures.

In contrast to conventional radical polymerization, controlled radicalpolymerization allows to adjust the molecular weight of all growingchains almost uniformly to a predetermined length (low polydispersity),resulting in an almost ideal dispersion of the intercalated and/orexfoliated clay particles.

The nanocomposite compositions of the instant invention can be opticallyalmost transparent, indicating the fine distribution, on the nanometerscale, of the clay.

One aspect of the invention is a compound of formula (I) or (II)

whereinG₁ and G₂ independently represent a tertiary carbon atom to whichunsubstituted C₁-C₁₈alkyl or phenyl or with CN, COC₁-C₁₈alkyl,CO-phenyl, COOC₁-C₁₈alkyl, OC₁-C₁₋₈alkyl, NO₂, NHC₁-C₁₈alkyl orN(C₁-C₁₈)₂alkyl substituted alkyl or phenyl groups are bonded; or one ofG₁ and G₂ is a secondary carbon atom to which a group —P(O)(OR₂₂)₂ andthe other is as defined above; orG₁ and G₂ together with the nitrogen atom to which they are bonded toform a 5 to 8 membered heterocyclic ring or a polycyclic or spirocyclic5 to 20 membered heterocyclic ring system, which is substituted with 4C₁-C₄alkyl groups or 2 C₅-C₁₂ spirocycloalkyl groups in ortho positionto the nitrogen atom and which may be further substituted with one ormore C₁-C₁₈alkyl, C₁-C₁₈alkoxy or ═O groups; andwhich may be interrupted by a further oxygen or nitrogen atom;with the proviso that at least one of the 4 C₁-C₄alkyl groups in orthoposition to the nitrogen atom is higher alkyl than methyl;L₁, L₂ and L₄ is a linking group selected from the group consisting of

-   -   a direct bond, R₁—Y or R₂—C(O)—Y— where Y is attached to G₁        and/or G₂; C₁-C₂₅alkylene, C₂-C₂₅alkylene interrupted by

-   -    phenylene and C₅-C₈cycloalkylene;    -   Y is O, or NR₉        L₃ is a group containing at least one carbon atom and is such        that the radical .L₃—(Q⁺X⁻) derived from the group is able to        initiate polymerization of ethylenically unsaturated monomers;        Q₂ is a direct bond, O, NR₅ or NR₅R₆;        Q⁺ is a cationic group selected from the group consisting of

-   -   wherein    -   R₁ is C₁-C₁₈alkylene,    -   R₂ is a direct bond or C₁-C₁₈alkylene,    -   R₃ is hydrogen or C₁-C₁₈alkyl,    -   R₄ is hydrogen or C₁-C₁₈alkyl,    -   R₅, R₆ and R₇ are each independently of the others hydrogen,        C₁-C₁₈alkyl, C₃-C₁₂cycloalkyl, phenyl or C₇-C₉phenylalkyl or        C₆-C₁₀heteroaryl which all may be unsubstituted or substituted        by halogen, OH, NO₂, CN, C₁-C₄alkoxy, or    -   R₅, R₆ and R₇ together with the nitrogen or phosphor atom to        which they are bonded form a 3-12 membered monocyclic or        polycyclic ring, which may contain further heteroatoms;    -   R₈ is hydrogen or C₁-C₂₅alkyl, C₃-C₂₅alkyl interrupted by        oxygen, sulfur or by

-   -    or C₂-C₂₄alkenyl,    -   R₉ is hydrogen, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl,        phenyl, C₇-C₉phenylalkyl, which all may be unsubstituted or        substituted by one or more hydroxy, halogen or C₁-C₄alkoxy        groups;    -   R₂₂ is C₁-C₁₈alkyl;    -   X⁻ is the anion of a C₁-C₁₈carboxylic acid which may contain        more than one carboxylic acid group, fluoride, chloride,        bromide, iodide, nitrite, nitrate, hydroxide, acetate, hydrogen        sulfate, sulfate, C₁-C₁₈alkoxy sulfate, aromatic or aliphatic        sulfonate, carbonate, hydrogen carbonate, perchlorate, chlorate,        tetrafluoroborate, borate, phosphate, hydrogenphosphate,        dihydrogenphosphate or mixtures thereof; and        p, q, and r are independently of each other a number from 0 to        10 and at least one is different from 0.

Alkyl having up to 18 carbon atoms is a branched or unbranched radical,for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetra-methylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.

C₃-C₁₈Alkyl interrupted by oxygen, sulfur or by

is, for example, CH₃—O—CH₂CH₂—, CH₃—S—CH₂CH₂—, CH₃—N(CH₃)—CH₂CH₂—,CH₃—O—CH₂CH₂—O—CH₂CH₂—, CH₃—(O—CH₂CH₂—)₂O—CH₂CH₂—,CH₃—(O—CH₂CH₂—)₃O—CH₂CH₂— or CH₃—(O—CH₂CH₂—)₄O—CH₂CH₂—.

C₇-C₉Phenylalkyl is, for example, benzyl, α-methylbenzyl,α,α-dimethylbenzyl or 2-phenylethyl. Preference is given to benzyl andα,α-dimethylbenzyl.

C₁-C₂₅Alkylene is a branched or unbranched radical, for examplemethylene, ethylene, propylene, trimethylene, tetramethylene,pentamethylene, hexamethylene, heptamethylene, octamethylene,decamethylene, dodecamethylene or octadecamethylene.

C₂-C₂₅alkylene interrupted by

phenylene or C₅-C₈cycloalkylene is, for example,

Alkenyl having 2 to 24 carbon atoms is a branched or unbranched radicalsuch as, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl,n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl,iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preference isgiven to alkenyl having 3 to 18, especially 3 to 12, for example 3 to 6,especially 3 to 4 carbon atoms.

Alkinyl having from 3 to 18 carbon atoms is a branched or unbranchedradical, for example propinyl, 2-butinyl, 3-butinyl, isobutinyl,n-2,4-pentadiinyl, 3-methyl-2-butinyl, n-2-octinyl, n-2-dodecinyl,isododecinyl.

Halogen is, for example, chlorine, bromine or iodine. Preference isgiven to chlorine and bromine.

Alkoxy having up to 25 carbon atoms is a branched or unbranched radical,for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy,pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy,tetradecyloxy, hexadecyloxy or octadecyloxy. Preference is given toalkoxy having from 1 to 12, especially from 1 to 8, e.g. from 1 to 6,carbon atoms.

Alkanoyloxy having up to 25 carbon atoms is a branched or unbranchedradical, for example acetoxy, propionyloxy, butanoyloxy, pentanoyloxy,hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy,undecanoyloxy, dodecanoyloxy, tridecanoyloxy, tetradecanoyloxy,pentadecanoyloxy, hexadecanoyloxy, heptadecanoyloxy, octadecanoyloxy,icosanoyloxy or docosanoyloxy. Preference is given to alkanoyloxy havingfrom 2 to 18, especially from 2 to 12, e.g. from 2 to 6, carbon atoms.

Hydroxyl-substituted C₂-C₁₈alkyl is a branched or unbranched radicalwhich contains preferably 1 to 3, in particular 1 or 2, hydroxyl groups,such as, for example, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl,4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, 5-hydroxypentyl,4-hydroxypentyl, 3-hydroxypentyl, 2-hydroxypentyl, 6-hydroxyhexyl,5-hydroxyhexyl, 4-hydroxyhexyl, 3-hydroxyhexyl, 2-hydroxyhexyl,7-hydroxyheptyl, 6-hydroxyheptyl, 5-hydroxyheptyl, 4-hydroxyheptyl,3-hydroxyheptyl, 2-hydroxyheptyl, 8-hydroxyoctyl, 7-hydroxyoctyl,6-hydroxyoctyl, 5-hydroxyoctyl, 4-hydroxyoctyl, 3-hydroxyoctyl,2-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 11-hydroxyundecyl,12-hydroxydodecyl, 13-hydroxytridecyl, 14-hydroxytetradecyl,15-hydroxypentadecyl, 16-hydroxyhexadecyl, 17-hydroxyheptadecyl,18-hydroxyoctadecyl.

C₅-C₁₂cycloalkyl is for example cyclopentyl, cyclohexyl, cycloheptyl,methylcyclopentyl or cyclooctyl.

If X⁻ is a monovalent radical of a saturated, unsaturated or aromaticcarboxylic acid, it is, for example, an acetyl, caproyl, stearoyl,acryloyl, methacryloyl, benzoyl orβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.

If X⁻ is a divalent radical of a dicarboxylic acid, it is, for example,a malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl,itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl,butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonyl orbicycloheptenedicarbonyl radical.

If X⁻ is a trivalent radical of a tricarboxylic acid, it is, forexample, a trimellitoyl, citryl or nitrilotriacetyl radical.

Heteroaryl is for example pyryl, thiophenyl, furyl, pyridyl orpyrimidyl.

When R₅, R₆ and R₇ form a monocyclic or polycyclic heterocyclic ring,the resulting cation is for example a pyridinium, quinolinium,isoquinolinium, imidazolium or thiazolium cation.

In one embodiment of the instant invention in formula I or II —L₁(Q⁺X⁻),—L₂(Q⁺X⁻), and —L₃(Q⁺X⁻), are a group

whereinK₁ and K₂ are hydrogen, C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, phenyl orC₇-C₉phenylalkyl andK₃ is a group

whereK₄ is —Y—[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻or—Y—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{[(CH₂—CH₂)—(CH₂)_(s)—N⁺X⁻R₅R₆]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻}_(u),where s is a number 0-8, t is a number 0-4 and u is 0 or 1 and Y is —O—or —NR₉; orK₄ is a group

Z is —C(O)— or a direct bond,if Z is —C(O)—, K₅ has the same meaning as K₄,if Z is a direct bond, K₅ isY—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻}_(u),Q⁺X⁻, —CH₂Q⁺X⁻ or CHCH₃Q⁺X⁻;and Y is —O— or —NR₉ or a direct bond;

the other substituents are as defined above.

Preferably the compounds are of formulae Ia, Ib, Ic, Id or Ie

whereinQ₁ is a direct bond or a —CH₂— group;if Q₁ is a direct bond, T₈ is hydrogen,if Q₁ is —CH₂—, T₈ is methyl or ethyl;T₁, T₂, T₃ and T₄ are independently methyl or ethyl with the provisothat at least one is ethyl;T₇ and T₁₀ are independently hydrogen or methyl;T₅ and T₆ are hydrogen orT₅ and T₆ together are a group ═O, ═NOH, ═NO—T₉ orT₅ is hydrogen and T₆ is —O—T₉ or —NR₉—T₉ where T₉ is hydrogen, R₉ or—C(O)—R₉, where R₉ is hydrogen, C₁-C₁₈alkyl, C₃-C₁₈alkenyl,C₃-C₁₈alkinyl, phenyl, C₇-C₉phenylalkyl, which may be unsubstituted orsubstituted by one or more hydroxy, halogen or C₁-C₄alkoxy groups;T₁₁, T₁₂, T₁₃, T₁₄, T₁₅ and T₁₆ independently are C₁-C₁₈alkyl,C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₅-C₁₂cycloalkyl, phenyl orC₇-C₉phenylalkyl; orT₁₁ is hydrogen and T₁₂ is a group —P(O)(OC₂H₅)₂ and the others are asdefined above;or T₁₁ and T₁₄ are a group —CH₂—O-T₉ and the others are as definedabove; orT₁₆ is a group —C(O)—Y—R₅ and the others are as defined above; orT₁₁, T₁₂ and T₁₃ are a group —CH₂OH;—L₃(Q⁺X⁻), is a group

whereinK₁ and K₂ are hydrogen, C₅-C₁₂cycloalkyl, phenyl or C₇-C₉phenylalkyl andK₃ is a group

whereK₄ is Y—[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻or—Y—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{[(CH₂—CH₂)—(CH₂)_(s)—N₊X⁻R₅R₆]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻}_(u),where s and t is a number 0-4 and u is 0 or 1; orK₄ is a group

Z is —C(O)— or a direct bond,if Z is —C(O)— K₅ has the meaning of K₄,if Z is a direct bond, K₅ isO—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{—[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻}_(u),Q⁺X⁻, —CH₂Q⁺X⁻ or —CHCH₃Q⁺X⁻;Y is —O— or —NR₉;

X⁻ and the other substituents are as defined above.

In another preferred embodiment of the invention the compounds are offormula IIa, IIb, IIc, IId or IIe

whereinA₁ and A₂ are independently hydrogen or together with the carbon atom towhich they are bonded form a carbonyl group, —C(O)—;D is a direct bond or C₁-C₁₂alkylene, C₁-C₁₂alkylene which isinterrupted by one or more O, S, or NR₉ atoms, C₅-C₁₂cycloalkylene orphenylene;E is a group —NR₉—(CH₂)_(k)—NR₉— where x is a number from 2 to 12 or agroup

v is a number from 0 to 10 and w is 0 or 1;Q₁ is a direct bond or a —CH₂— group;if Q₁ is a direct bond, T₈ is hydrogen,if Q₁ is —CH₂—, T₈ is hydrogen, methyl or ethyl;Y is —O— or —NR₉;T₁, T₂, T₃ and T₄ are independently methyl or ethyl with the provisothat at least one is ethyl;T₇ is hydrogen or methyl;—L₃(Q⁺X⁻), is a group

whereinK₁ and K₂ are hydrogen, C₅-C₁₂cycloalkyl, phenyl or C₇-C₉phenylalkyl andK₃ is a group

whereK₄ is Y—[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻or—Y—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻}_(u),where s and t is a number 0-4 and u is 0 or 1; orK₄ is a group

Z is —C(O)— or a direct bond,if Z is —C(O)— K₅ has the meaning of K₄,if Z is a direct bond, K₅ isO—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻}_(u),Q⁺X⁻, —CH₂Q⁺X⁻ or —CHCH₃Q⁺X⁻;

X⁻ and the other substituents are as defined above.

Also preferred are the compounds of formula IIIa, IIIb, IIIc, IIId orIIIe

T₁, T₂, T₃ and T₄ are independently methyl or ethyl with the provisothat at least one is ethyl;T₇ is hydrogen or methyl;Y is O or NR₉;Q₁ is a direct bond or a —CH group;if Q₁ is a direct bond, T₈ is hydrogen,if Q₁ is —CH₂—, T₈ is methyl or ethyl;v is a number from 0 to 10 and w is 0 or 1;K₇ is a group—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻}_(u),where s and t is a number 0-4 and u is 0 or 1; or a group —D₁—Q⁺X⁻ whereD₁ is C₁-C₁₂alkylene, C₁-C₁₂alkylene which is interrupted by one or moreO, S, or NR₉ atoms, C₅-C₁₂cycloalkylene or phenylene;

K₆ is selected from the group consisting of

R₃₀ is hydrogen or C₁-C₁₂alkyl;the alkyl groups are unsubstituted or substituted with one or more —OH,—COOH or —C(O)R₃₀ groups; andthe aryl groups are phenyl or naphthyl which are unsubstituted orsubstituted with C₁-C₁₂alkyl, halogen, C₁-C₁₂alkoxy,C₁-C₁₂alkylcarbonyl, glycidyloxy, OH, —COOH or —COO(C₁-C₁₂)alkyl andX⁻ and the other substituents are as defined above.

Particularly suitable are the compounds according to formula IVa

whereinT₁, T₂, T₃ and T₄ are independently methyl or ethyl with the provisothat at least one is ethyl;T₇ is hydrogen or methyl;

where x is a number from 2 to 12;K₆ is selected from the group consisting of

R₃₀ is hydrogen or C₁-C₁₂alkyl;the alkyl groups are unsubstituted or substituted with one or more —OH,—COOH or —C(O)R₃₀ groups; andthe aryl groups are phenyl or naphthyl which are unsubstituted orsubstituted with C₁-C₁₂alkyl, halogen, C₁-C₁₂alkoxy,C₁-C₁₂alkylcarbonyl, glycidyloxy, OH, —COOH or —COO(C₁-C₁₂)alkyl andX⁻ and the other substituents are as defined above.

Preference is also given to compounds of formula Va, Vb, Vc, Vd or Ve

whereinT₁, T₂, T₃ and T₄ are independently methyl or ethyl with the provisothat at least one is ethyl;T₇ is hydrogen or methyl;Q₁ is a direct bond or a —CH₂— group;if Q₁ is a direct bond, T₈ is hydrogen,if Q₁ is —CH₂—, T₈ is methyl or ethyl;K₁ and K₂ are hydrogen, C₅-C₁₂cycloalkyl, phenyl or C₇-C₉phenylalkyl andK₃ is a group

whereK₄ is Y—[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻or—Y—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)₅—N⁺R₅R₆R₇X⁻}_(u),where s and t is a number 0-4 and u is 0 or 1; orK₄ is a group

Z is —C(O)— or a direct bond,if Z is —C(O)— K₅ has the meaning of K₄,if Z is a direct bond, K₅ isO—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{[(CH₂—CH₂)—(CH₂)₅—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻}_(u),Q⁺X⁻, —CH₂Q⁺X⁻ or —CHCH₃Q⁺X⁻;K₇ is a group—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻}_(u),where s and t is a number 0-4 and u is 0 or 1; or a group —D₁—Q⁺X⁻ whereD₁ is C₁-C₁₂alkylene, C₁-C₁₂alkylene which is interrupted by one or moreO, S, or NR₉ atoms, C₅-C₁₂cycloalkylene or phenylene;

X⁻ and the other substituents are as defined above.

Also preferred are compounds of formula VIa

whereinT₁, T₂, T₃ and T₄ are independently methyl or ethyl with the provisothat at least one is ethyl;T₇ is hydrogen or methyl;

where x is a number from 2 to 12;K₁ and K₂ are hydrogen, C₅-C₁₂cycloalkyl, phenyl or C₇-C₉phenylalkyl andK₃ is a group

whereK₄ is Y—[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(r)—N⁺R₅R₆R₇X⁻or—Y—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻}_(u),where s and t is a number 0-4 and u is 0 or 1; orK₄ is a group

Z is —C(O)— or a direct bond,if Z is —C(O)— K₅ has the meaning of K₄,if Z is a direct bond, K₅ isO—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻}_(u),Q⁺X⁻, —CH₂Q⁺X⁻ or —CHCH₃Q⁺X⁻ andX⁻ and the other substituents are as defined above.

Of particular interest are compounds of formula Ia1, Ib1, Ic1, Id1 orIe1

whereinQ₁ is a direct bond or CH₂;T₁, T₃ are ethyl and T₂, T₄ are methyl;T₇ is methyl or H;if Q₁ is a direct bond, T₈ is H;if Q₁ is CH₂, T₈ is methyl or ethyl;T₁₀ is H if T₇ is methyl or T₁₀ is methyl if T₇ is H;T₁₁, T₁₂, T₁₃, T₁₄, T₁₅ and T₁₆ are independently methyl or ethyl; orT₁₁ is H, T₁₂ is isopropyl, T₁₃ is phenyl and T₁₄, T₁₅, T₁₆ are methyl;orT₁₁ is H, T₁₂ is —P(═O)(OC₂H₅)₂, T₁₃ is t-butyl and T₁₄, T₁₅, T₁₆ aremethyl; orT₁₁ and T₁₄ are —CH₂O-T₉ and T₁₂, T₁₅ are methyl or phenyl and T₁₃, T₁₆are methyl or ethyl; orT₁₁, T₁₂, T₁₃, T₁₄, T₁₅ are methyl and T₁₆ is a group —CO—O—R₉ orCON(R₉)₂; orT₁₁, T₁₂ and T₁₃ are —CH₂OH, T₁₄ is H, T₁₅ is isopropyl and T₁₆ phenyl;T₉ is hydrogen, R₉ or —C(O)—R₉, where R₉ is hydrogen, C₁-C₁₈alkyl,C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, phenyl, C₇-C₉phenylalkyl;K₁ is H, K₂ is methyl or ethyl andK₃ is a group

K₄ is —Y—CH₂—CH₂—(CH₂)_(r)—N⁺X⁻R₅R₆R₇ or;—Y—CH₂—CHOH—CH₂—N—CH₂—CH₂—(CH₂)_(s)—N⁺X⁻R₅R₆R₇ where Y is O or NR₉ and sis a number from 0 to 2;if K₃ is

Z is —CO— or a direct bond;if Z is —CO—, K₅ has the same meaning as K₄;if Z is a direct bond, K₅ is a group—O—CH₂—CHOH—CH₂—N—CH₂—CH₂—(CH₂)_(s)—N⁺X⁵R₅R₆R₇ or —CH₂N⁺R₅R₆R₇X⁻ andX⁻ and the other substituents are as defined above.

Also of particular interest are compounds of formula IIa1, IIb1, IIc1 orIId1

whereinQ₁ is a direct bond or CH₂;T₁, T₃ are ethyl and T₂, T₄ and T₇ are methyl;if Q₁ is a direct bond, T₈ is H;if Q₁ is CH₂, T₈ is methyl or ethyl;D is a direct bond, C₁-C₁₂alkylene or phenylene;E is —NR₅—(CH₂)_(x)—NR₅— where x is 2 to 12 or a group

wherein Y is ═NR₉K₁ is H, K₂ is methyl or ethyl andK₃ is a group

K₄ is —Y—CH₂—CH₂—(CH₂)_(s)—N⁺X⁻R₅R₆R₇ or;—Y—CH₂—CHOH—CH₂—N—CH₂—CH₂—(CH₂)_(s)—N⁺X⁻R₅R₆R₇ where Y is O or NR₉ and sis a number from 0 to 2;if K₃ is

or a direct bond;if Z is —CO— K₅ has the same meaning as K₄;if Z is a direct bond K₅ is a group—O—CH₂—CHOH—CH₂—N—CH₂—CH₂—(CH₂)_(s)—N⁺X⁻R₅R₆R₇ or —CH₂N⁺R₅R₆R₇X⁻; andX⁻ and the other substituents are as defined above.

The precursors of the above compounds can be prepared according to knownmethods.

The preparation of open chain alkoxyamines is for example described inWO 99/03894 or in WO 00/07981. Alkoxyamines based on tetraalkylpiperidine are for example described in GB 2 335 1290 or in GB 2 361235. Further heterocyclic alkoxyamines are described in GB 2 342 649.

A very suitable, but not the only possible, method for the introductionof the cationic moiety into the molecule of the alkoxyamine consists offirst preparing the suitable precursor alkoxyamine which is thenquarternised. Examples of such alkoxyamines are given in the examples inTable 1. The non cationic precursors can be prepared by a variety ofmethods described in the cited patents using the suitable buildingblocks bearing the appropriate nucleophilic groups capable ofquarternisation. Few examples of such groups are primary, secondary ortertiary amine group, pyridyl, quinolyl, isoquinolyl, imidazolyl,thiazolyl groups, trialkyl or triaryl or alkylarylphosphine groups or athioether group. These can be quarternised by a variety of electrophilicreagents, for example alkyl halides, alkyl sulfonates, alkyl carbonates,trialkyloxonium salts, epoxides or others. A special case is theformation of the cationic moiety by protonation of the citednucleophilic groups by their protonation with acids. A given specificanion of the cationic alkoxyamine can be exchanged against a differentone using for example ion exchangers or well known ion metathesis.

A further aspect of the invention is a process for preparing amonomer/polymer clay nanocomposite dispersion comprising the steps of

-   -   A) providing a first aqueous dispersion of a natural or        synthetic clay which can be partially intercalated and/or        exfoliated and wherein said clay has an exchangeable cation;        -   adding a compound according to claim 1 to said dispersion            and exchanging said cation at least partially;    -   B) adding to said dispersion at least one ethylenically        unsaturated monomer and polymerizing at least a portion of said        ethylenically unsaturated monomer.

Clay minerals are typically comprised of hydrated aluminum silicatesthat are fine-grained and have a platy habit. The crystalline structureof a typical clay mineral is a multi-layered structure comprised ofcombinations of layers of SiO₄ tetrahedra that are joined to layers ofAlO(OH)₂ octahedra. A so called “gallery” is formed which describes thedefined interlayer spaces of the layered clay minerals. Depending on theclay mineral the gallery may contain water and/or other constituentssuch as potassium, sodium or calcium cations. Clay minerals vary basedupon the combination their constituent layers and cations. Isomorphicsubstitution of the cations of clay mineral, such as Al³⁺ or Fe³⁺substituting for the Si⁴⁺ ions in the tetrahedral network, or Al³⁺, Mg²⁺or Fe²⁺ substituting for other cations in the octahedral network,typically occurs and may impart a net negative charge on the claystructure. Natural occurring elements within the gallery of the clay,such as water molecules or sodium or potassium cations, are attracted tothe surface of the clay layers due to this net charge.

Nanocomposites are compositions in which at least one of itsconstituents has one or more dimensions, such as length, width orthickness in the nanometer size range. The term nanocomposite, as usedherein, denotes the state of matter wherein polymer molecules existamong at least partially exfoliated clay layers.

The term “intercalated nanocomposite”, as used herein describes ananocomposite that contains a regular insertion between the clay layers.

The term “exfoliated nanocomposite” as used herein describes ananocomposite wherein the 1 nm thick layers of clay are dispersed in thematrix (oligomer/polymer) forming a composite structure on thenano/micro scale.

The clay minerals are items of commerce and are for example supplied bySüd-Chemie Inc., Germany.

Preferably the ethylenically unsaturated monomer or oligomer is selectedfrom the group consisting of ethylene, propylene, n-butylene,i-butylene, styrene, substituted styrene, conjugated dienes, acrolein,vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride,(alkyl)acrylic acid anhydrides, (alkyl)acrylic acid salts,(alkyl)acrylic esters, (meth)acrylonitriles, (alkyl)acrylamides, vinylhalides or vinylidene halides.

Particularly the ethylenically unsaturated monomers are ethylene,propylene, n-butylene, i-butylene, isoprene, 1,3-butadiene,α-C₅-C₁₈alkene, styrene, α-methyl styrene, p-methyl styrene or acompound of formula CH₂═C(R_(a))—(C=Z)-R_(b), wherein R_(a) is hydrogenor C₁-C₄alkyl, R_(b) is NH₂, O⁻(Me⁺), glycidyl, unsubstitutedC₁-C₁₈alkoxy, C₂-C₁₀₀alkoxy interrupted by at least one N and/or O atom,or hydroxy-substituted C₁-C₁₉alkoxy, unsubstituted C₁-C₁₈alkylamino,di(C₁-C₁₈alkyl)amino, hydroxy-substituted C₁-C₁₈alkylamino orhydroxy-substituted di(C₁-C₁₈alkyl)amino, O—CH₂—CH₂—N(CH₃)₂ or—O—CH₂—CH₂—N⁺H(CH₃)₂An⁻;

An⁻ is a anion of a monovalent organic or inorganic acid;

Me is a monovalent metal atom or the ammonium ion.

Z is oxygen or sulfur.

Examples for R_(a) as C₂-C₁₀₀alkoxy interrupted by at least one O atomare of formula

wherein R_(c) is C₁-C₂₅alkyl, phenyl or phenyl substituted byC₁-C₁₈alkyl, R_(d) is hydrogen or methyl and v is a number from 1 to 50.These monomers are for example derived from non ionic surfactants byacrylation of the corresponding alkoxylated alcohols or phenols. Therepeating units may be derived from ethylene oxide, propylene oxide ormixtures of both.

Further examples of suitable acrylate or methacrylate monomers are givenbelow.

wherein An⁻ and R_(a) have the meaning as defined above and R_(e) ismethyl or benzyl. An⁻ is preferably Cl⁻, Br⁻ or ⁻O₃S—CH₃.

Further acrylate monomers are

Examples for suitable monomers other than acrylates are

Preferably R_(a) is hydrogen or methyl, R_(b) is NH₂, glycidyl,unsubstituted or with hydroxy substituted C₁-C₄alkoxy, unsubstitutedC₁-C₄alkylamino, di(C₁-C₄alkyl)amino, hydroxy-substitutedC₁-C₄alkylamino or hydroxy-substituted di(C₁-C₄alkyl)amino; and

Z is oxygen.

Also suitable ethylenically unsaturated monomers are styrene,methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert.butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate,dimethylaminoethylacrylate, glycidylacrylates, methyl(meth)acrylate,ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,glycidyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide ordimethylaminopropyl-methacrylamide.

Preferred is a process wherein the ethylenically unsaturated monomer isselected from the group consisting of C₁-C₁₈ alkyl methacrylate, C₁-C₁₈alkyl acrylate, 2-ethylhexyl (meth)acrylate, isobornyl(meth)acrylate,lauryl(meth)acrylate, allyl(meth)acrylate, stearyl (meth)acrylate,acrylic acid, itaconic acid, methacrylic acid, butadiene, vinyl acetate,vinyl versa tate, styrene, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, vinyl aromatic monomers, divinylbenzene,divinylpyridine, divinyltoluene, diallyl phthalate, ethylene glycoldi(meth)acrylate, butylene glycol di(meth)acrylate, divinylxylene,divinylethylbenzene, divinylsulfone, divinylketone, divinylsulfide,diallyl maleate, diallyl fumarate, diallyl succinate, diallyl carbonate,diallyl malonate, diallyl oxalate, diallyl adipate, diallyl sebacate,divinyl sebacate, diallyl tartrate, diallyl silicate, triallyltricarballylate, triallyl aconitate, triallyl citrate, triallylphosphate, N,N-methylene dimethacrylamide, N,N-methylenedimethacrylamide, N,N-ethylenediacrylamide, trivinylbenzene, and thepolyvinyl ethers of glycol, glycerol, pentaerythritol, resorcinol,monothio and dithio derivatives of glycols, and combinations thereof.

Special preference is given to a process wherein an acid containingunsaturated monomer is added, which is selected from the groupconsisting of methacrylic anhydride, maleic anhydride, itaconicanhydride, acrylic acid, methacrylic acid, itaconic acid, maleic acid,fumaric acid, acryloxypropionic acid, (meth)acryloxypropionic acid,styrene sulfonic acid, ethylmethacrylate-2-sulphonic acid,2-acrylamido-2-methylpropane, sulphonic acid; phosphoethylmethacrylate;the corresponding salts of the acid containing monomer, and combinationsthereof.

In one embodiment of the invention the process is carried out whereinthe water phase of step A) is at least partially removed beforeperforming step B).

It is also possible that in step B) an organic solvent is additionallyadded.

Preferred is a process wherein the polymerization is carried out byapplying heat, at a temperature of from 60° C. to 160° C.

Preferred is a process wherein the compound of formula I or II is addedin an amount of from 1% to 100% by weight, based on the weight of theclay.

Preferably the weight ratio between the ethylenically unsaturatedmonomer added in step B) and the clay of step A) which is at leastpartially intercalated with a compound of formula I or II is from 500:1to 1:5.

In a specific embodiment of the invention the process is carried outwherein a further cationic compound selected from the group of cationicsurfactants is added in step A).

Typical surfactants are amino acids or alkylammonium ions.

The amino acid surfactants transfer a proton from the COOH group to theNH₂ group forming a NH₃ ⁺ group which can exchange with a cation of theclay mineral.

For example the alkylammonium ion is CH₃—(CH₂)_(n)—NH₃ ⁺ where n is from1 to 18. It is believed that the alkylammonium cations readily exchangewith the naturally occurring cations present inbetween the clayplatelets resulting in an intercalated state.

It is also possible to repeat the process step B) with a secondethylenically unsaturated monomer which is different from the first one,leading to a block copolymer.

The clay may be a natural or synthetic clay material.

When the clay material is a synthetic one, it may be produced bygas-phase or sol-gel processes, for example SiO₂, [e.g. Aerosil® fromDegussa; Ludox® from DuPont; Snowtex® from Nissan Chemical; Levasil®from Bayer; or Sylysia® from Fuji Silysia Chemical]; colloidal silica[e.g. Klebosol®], or organosols [e.g. Highlink® OG from Clariant].

Typical clays are natural or synthetic phyllosilicates, which may beorganophilically modified montmorillonites [e.g. Nanomer® from Nanocoror Nanofil® from Suedchemie], bentonites [e.g. Cloisite® from SouthernClay Products], beidellites, hectorites, saponites, nontronites,sauconites, vermiculites, ledikites, magadiites, kenyaites orstevensites.

These materials are commercially available in its natural or partiallyintercalated form.

Special preference is given to a process wherein the natural orsynthetic clay is selected from the group consisting of smectite,phyllosilicate, montmorillonite, saponite, beidellite, montronite,hectorite, stevensite, vermiculite, kaolinite, hallosite, syntheticphyllosilicates, and combinations thereof.

Most preferred is montmorillonite.

Further aspects of the invention are a monomer/polymer claynanocomposite dispersion obtainable by a process as described above, acomposition comprising an aqueous dispersion of a natural or syntheticclay which is partially intercalated and/or exfoliated and a compound asdescribed above and a composition, which contains additionally anethylenically unsaturated monomer and/or a organic solvent.

Yet another aspect of the invention is the use of a compound of formulaI or II for the polymerization of ethylenically unsaturated monomers andthe use of a monomer/polymer clay nanocomposite dispersion obtainableaccording to the process as defined above as additive in paints,coatings, inks, adhesives, reactive diluents or in thermoplasticmaterials.

The following examples illustrate the invention.

A) PREPARATION EXAMPLES OF THE COMPOUNDS Example A1{4-[1-(4-tert-butyl-2,2-diethyl-6,6-dimethyl-3-oxo-piperazine-1-yloxy)-ethyl]-benzyl}-triethyl-ammoniumchloride (Compound 101, Table 1) a)1-tert-butyl-4-[1-(4-chloromethyl-phenyl)-ethoxy]-3,3-diethyl-5,5-dimethyl-piperazine-2-one

To a solution of 13.4 g (0.052 mol)1-tert-butyl-3,3-diethyl-5,5-dimethyl-piperazine-2-one-4-N-oxyl(prepared according to Ger. Offen. DE 19949352 A1) and 8 g (0.052 mol)4-chloromethylstyrene in 320 ml ethanol 5 g (0.00788 mol) (S,S)-Jacobsencatalyst are added. Thereafter 9.6 ml (0.052 mol) t-butylhydroperoxide(70% in H₂O) are added followed by 4 g (0.010 mol) sodiumborohydride.The mixture is stirred at room temperature under argon for 20 h andsubsequently evaporated under vacuum. The residue is diluted with 50 mlwater and then extracted with 2×50 ml dichlormethane. The extract isdried over MgSO₄ and purified by chromatography on silica gel(hexane-ethylacetate 12:1). After crystallisation of the pure fractionfrom pentane 4.5 g of the title compound are obtained, mp. 66-68° C.

C₂₃H₃₇ClN₂O₂ (409.02) calculated: C, 67.54%; H, 9.12%; N, 6.85. found:C, 67.58%; H, 9.16%; N, 6.77%.

b) Quaternisation

To a solution of 20 ml triethylamine in 20 ml acetonitrile 4 g (0.0098mol) of the product obtained under a) are added. The solution is stirredfor 10 h at 60° C. and evaporated. The solid residue is suspended in 30ml t-butyl-methyl-ether, filtrated and dried. 4.7 g of the titlecompound are obtained as a white powder.

¹H-NMR (300 MHz, CDCl₃): 7.57-7.49 m (2ArH), 7.41-7.38 m (2 ArH),4.93-4.69 m (3H), 3.57-3.37 m (6H), 3.21-2.93 m (2H), 2.0-0.62 m (37H).

Example A24-{4-[1-(4-tert-butyl-2,2-diethyl-6,6-dimethyl-3-oxo-piperazine-1-yloxy)-ethyl]-benzoyl}-1,1-dimethyl-piperazine-1-iumiodide (Compound 102, Table 1) a)1-tert-butyl-3,3-diethyl-5,5-dimethyl-4-{1-[4-(4-methyl-piperazine-1-carbonyl)-phenyl]-ethoxy}-piperazine-2-one

To a solution of 0.5 g (0.00124 mol)4-[1-(4-.tert.-butyl-2,2-diethyl-6,6-dimethyl-3-oxo-piperazin-1-yloxy)-ethyl]-benzoicacid (prepared according to WO 01/02345 A2) in 10 ml dichlormethane 0.4g (0.00248 mol) carbonyldiimidazol are added. The mixture is stirred for30 minutes under argon at room temperature. Subsequently 0.275 ml(0.00248 mol) N-methylpiperazine is added and the solution is stirredfor further 12 h. The solution is then washed 3× with 5 ml water, driedover MgSO₄, and evaporated. The residue is purified by chromtography onsilica gel (hexane-ethylacetate 2:1) and 0.46 g of the title compoundare obtained as viscous oil.

¹H-NMR (300 MHz, CDCl₃): 7.39-7.28 m (4 ArH), 4.75-4.69 m (1H), 4-0.65 m(41H).

b) Quaternisation

To a solution of 1 g (0.002 mol) of the product obtained under a) in 2ml acetonitrile 2 ml methyliodide are added and the solution is stirredat room temperature for 1 h. After evaporation 1.2 g of the titlecompound are obtained as yellow powder.

¹H-NMR (300 MHz, DMSO-d₆): 7.45 s (4 ArH), 4.79-4.73 m (1H), 4.1-0.58 m(43H).

Example A3{3-[2-(2,6-diethyl-2,3,6-trimethyl-piperidine-1-yloxy)-propionylamino]-propyl}ethyl-dimethyl-ammoniumbromide (Compound 103, Table 1) a)2-chloro-N-(3-dimethylamino-propyl)-propionamide

To 12.25 g (0.1 mol) 2-chlorpropionic acid-methylester 10.25 g (0.1 mol)3-dimethylamino-1-propylamine are added at such a rate, that thereaction temperature remains below 40° C. The mixture is stirred for 4 hat room temperature and subsequently evaporated at 40° C./1 mbar.Thereafter, the methanol formed in the reaction is distilled off. 18.4 gof the title compound are obtained as colorless oil.

¹H-NMR (300 MHz, CDCl₃): 8.47 bs (NH), 4.41-4.34 q (1H), 3.40-3.34 m(2H), 2.47-2.40 m (2H), 2.24 s (6H), 1.70-1.68 d (3H), 1.73-1.64 m (2H)

b)2-(2,6-diethyl-2,3,6-trimethyl-piperidine-1-yloxy)-N-(3-dimethylamino-propyl)-propionamide

To a solution of 13.85 g (0.07 mol)2,6-Diethyl-2,3,6-trimethyl-piperidin-1-N-oxyl (prepared according toGer. Offen. DE 2621841) in 70 ml ethylacetate 13.9 g (0.14 mol)Cu(I)-chloride are added under argon followed by 24.25 g (0.14 mol)pentamethyldiethylentriamine (PMDETA). Subsequently within 10 minutes14.95 g (0.0735 mol) of the product obtained under a) are addeddropwise. The mixture is stirred at room temperature for 12 h, followedby further addition of 3.05 g of the chloramide prepared under a), 2 gCuCl and 4.3 ml PMDETA, 20 ml ethylacetate and 10 ml DMF. The mixture isthen stirred for further 96 h at room temperature. The suspension isfiltered and the filter cake is washed with 100 ml ethylacetate. Thefiltrate is washed with 3×100 ml water, then with 2×60 ml of a 1%aqueous EDTA-disodiumsalt-solution and dried over MgSO₄. The residue ispurified by chromatography on silica gel (hexane-ethylacetate 2:1). 7.7g of the title compound are obtained as thick yellow oil.

C₂₀H₄₁N₃O₂ (355.8) found: MH⁺=356.3 (APCI-MS).

c) Quaternisation

To a solution of 7.6 g (0.0214 mol) of the product obtained under b) in10 ml acetonitrile 10 ml ethylbromide are added and the solution isstirred for 12 h at room temperature. After evaporation 9 g of the titlecompound are obtained as white powder.

For [C₂₂H₄₆N₃O₂]⁺×Br⁻=[384.64]×[79.904]. found M⁺ (Cation)=384.6(Infusion ESI-MS)

Example A4{3-[2-(2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-1-yloxy)-propionylamino]-propyl}-ethyl-dimethyl-ammoniumbromide (Compound 104, Table 1) a)2-(2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-1-yloxy)-.N.-(3-dimethylamino-propyl)-propionamide

To a solution of 21.4 g (0.1 mol)2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-1-N-oxyl (preparedaccording to Ger. Offen. DE 19909767 A1) in 50 ml DMF 19.8 g (0.2 mol)Cu(I)-chloride are added under argon. Subsequently 34.7 g (0.2 mol)pentamethyldiethylentriamine (PMDETA) and 22.1 g (0.11 mol)2-chloro-N-(3-dimethylamino-propyl)-propionamide (prepared according toexample A3) are added within 20 minutes. The temperature during additionis kept below 40° C. The mixture is stirred 4 h at room temperaturefollowed by the addition of 500 ml water and 150 ml dichlormethane. Theorganic phase is separated and the water phase is extracted with 2×100ml dichlormethane. The organic phases are washed with 5×100 ml water,then with 3×60 ml 1% aqueous EDTA-Disodiumsalt-solution, dried overMgSO₄ evaporated. 33.55 g of the title compound are obtained as thickyellow oil.

¹H-NMR (300 MHz, CDCl₃): 7.34-7.14 bs (1H), 4.29-4.20 m (2H), 3.6-3.1 m(2H), 2.6-0.83 m (30H), 2.22 s (6H).

b) Quaternisation

To a solution of 28.35 g (0.076 mol) of the product obtained under a) in25 ml acetonitrile 25 ml ethylbromide are added and the solution isstirred for 12 h at room temperature. After evaporation 36.5 g of thetitle compound are obtained as white powder.

For [C₂₂H₄₆N₃O₃]⁺×Br⁻=[400.626]×[79.904]. found M⁺ (Kation)=400.4(Infusion ESI-MS)

Example A5[3-(2-{.N.-.tert.-butyl-.N.-[1-(diethoxy-phosphoryl)-2,2-dimethyl-propyl]-aminooxy}-propionylamino)-propyl]-ethyl-dimethyl-ammoniumbromide (Compound 105, Table 1) a)(1-{.tert.-butyl-[1-(3-dimethylamino-propylcarbamoyl)-ethoxy]-amino}-2,2-dimethyl-propyl)-phosphonicacid diethyl ester

From 5.01 g (0.017 mol)N-(1,1-Dimethylethyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl(prepared according to Macromolecules (2000), 33(4), 1141-1147), 3.35 g(0.034 mol) CuCl, 5.9 g (0.034 mol) PMDETA and 3.95 g (0.0196 mol)2-chloro-N-(3-dimethylamino-propyl)-propionamide (prepared according toexample A3) in 10 ml DMF 5.6 g of the title compound are obtained asthick yellowish oil in analogy to example A4 (reaction time 19 h).

For C₂₁H₄₆N₃O₅P (451.59) calculated C, 55.85%; H, 10.27%; N, 9.31%.found C, 55.09%; H, 9.91%; N, 8.86%.

b) Quaternisation

To a solution of 4.95 g (0.011 mol) of the product obtained under a) in23 ml acetonitrile 3.3 ml ethylbromide are added and the solution isstirred for 17 h at room temperature. The suspension is evaporated, theresidue is suspended in 25 ml diethylether and filtered. 5.45 g of thetitle compound are obtained as a white powder.

Example A6{3-[2,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-ylidene-aminooxy]-propyl}ethyl-dimethyl-ammonium-bromide(Compound 106, Table 1) a)2,6-Diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one-O-(3-dimethylamino-propyl)-oxime

To a slurry of sodium hydride (4.36 g, 0.1 mol, 55% in mineral oil) inDMF (30 ml) is added dropwise the solution of2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one oxime(16.6 g, 0.05 mol, prepared as described in WO 02/100831 A1). Themixture is stirred 150 min at 25° C. and then3-dimethylaminopropylchloride (9.48 g, 0.06 mol) is added during 1 h.The mixture is stirred at room temperature for 18 h, the DMF is thenevaporated in vacuo. The residue is dissolved in ethyl acetate (100 ml),washed with water (2×25 ml), dried over MgSO₄ and evaporated.Chromatography on silica gel column (hexane-ethylacetate 1:1) affords12.55 g of the title compound as a colorless oil.

MS (DEP-Cl), C₂₅H₄₃N₃O₂ (417.64): found 418 (100, [M+H]⁺).

b) Quaternisation

Ethylbromide (7.5 ml) is added to a solution of2,6-diethyl-2,3,6-trimethyl-1-(1-phenyl-ethoxy)-piperidine-4-one-O-(3-dimethylamino-propyl)-oxime(10.2 g, 0.0244 mol) in acetonitrile (12 ml). The solution is stirred 24h at room temperature and is then evaporated. The residue is dissolvedin dichloromethane, dried over MgSO₄ and evaporated to afford 11.5 g ofthe title compound as a white powder.

MS (ESI), cation C₂₇H₄₈N₃O₂ (446.4): found 446.9.

Example A7{3-[2-(2,6-Diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-1-yloxy)-propionyl-amino]-propyl}-ethyl-dimethyl-ammonium-bromide-terephthalate(Compound 107, Table 1) a) Terephthalic acidbis-(2,6-diethyl-2,3,6-trimethyl-piperidine-N-oxyl-4-yl)ester

Terephthaloylchloride (12.2 g, 0.06 mol) is added dropwise to a solutionof 2,6-diethyl-2,3,6-trimethyl-piperidine-4-hydroxy-N-oxyl (25.72 g,0.12 mol, prepared as described in DE 19909767 A1) in dichloromethane(80 ml) and pyridine (30 ml). The mixture is stirred 72 h, is thendiluted with dichloromethane (100 ml) and water (100 ml). The organiclayer is washed with water (2×50 ml), dried over MgSO4 and evaporated.The residue is chromatographed on silica gel column (500 g,hexanes-ethylacetate 4:1) to afford 31.85 g of the title compound as athick red oil.

b) Terephthalic acidbis-{1-[1-(3-dimethylamino-propylcarbamoyl)-ethoxy]-2,6-diethyl-2,3,6-trimethyl-piperidine-4-yl}ester

Terephthalic acidbis-(2,6-diethyl-2,3,6-trimethyl-piperidine-N-oxyl-4-yl) ester (16.76 g,0.03 mol), CuCl (11.9 g, 0.12 mol), PMDETA (20.8 g, 0.12 mol) and2-chloro-N-(3-dimethylami-no-propyl)-propionamide (13.7 g, 0.071 mol)are reacted as described in Example A3 to afford 21.1 g of the titlecompound as amorphous solid.

MS (APCI), C₄₈H₈₄N₆O₈ (873.24): found M⁺=872.8.

c) Quaternisation

Ethylbromide (7.5 ml) is added to a solution of terephthalic acidbis-{1-[1-(3-dimethylami-no-propylcarbamoyl)-ethoxy]-2,6-diethyl-2,3,6-trimethyl-piperidine-4-yl}ester(11.0 g, 0.0125 mol) in acetonitrile (20 ml). The mixture is stirred atroom temperature for 17 h and is then evaporated to afford 14.1 g of thetitle compound as a colorless amorphous solid.

MS (ESI), cation C₅₂H₉₄N₆O₈ (930.7): found 931.8.

Example A8Ethyl-{3-[2-(4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-yloxy)-propionylamino]-propyl}-dimethyl-ammonium-bromide(Compound 108, Table 1) a)N-(3-Dimethylamino-propyl)-2-(4-hydroxy-2.2,6,6-tetramethyl-piperidine-1-yloxy)-propionamide

4-Hydroxy-TEMPO (25.84 g, 0.15 mol), CuCl (29.7 g, 0.3 mol), PMDETA(52.0 g, 0.3 mol) and 2-chloro-N-(3-dimethylamino-propyl)-propionamide(35.75 g, 0.18 mol) are reacted as described in Example A3. The finalpurification of the residue after the extractive workup is performed bycrystallization from toluene (45 ml) and hexane (50 ml) to afford 31.13g of the title compound as a white solid, mp. 85-88° C.

For C₁₇H₃₅N₃O₃ (329.49) calc %/found %: C, 61.97/61.85; H, 10.71/10.55;N, 12.75/12.61.

b) Quaternisation

Ethylbromide (9.85 ml) is added to a solution ofN-(3-dimethylaminopropyl)-2-(4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-yloxy)-propionamide(10.9 g, 0.033 mol) in acetonitrile (30 ml). The mixture is stirred atroom temperature for 22 h and is then evaporated to afford 14.7 g of thetitle compound as a colorless amorphous solid.

MS (ESI) cation C₁₉H₄₀N₃O₃ (358.3): found 358.6.

Example A9{3-[2-(2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-1-yloxy)-2-methyl-propionylamino]-propyl}-ethyl-dimethyl-ammonium-bromide(Compound 109, Table 1)

Ethylbromide (12 ml) is added to a solution of2-(2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-1-yloxy)-N-(3-dimethylamino-propyl)-2-methyl-propionamide(20.5 g, 0.053 mol, compound 110) in acetonitrile (35 ml). The mixtureis stirred for 18 h at room temperature and is then evaporated to afford26.63 g of the title compound as a colorless solid.

MS (ESI) cation C₂₃H₄₈N₃O₃ (414.4): found 414.5.

Example A102-(2,6-Diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-1-yloxy)-.N.-(3-dimethylamino-propyl)-2-methyl-propionamide(Compound 110, Table 1) a)2-Bromo-N-(3-dimethylamino-propyl)-2-methyl-propionamide

To a solution of 3-dimethylaminopropylamine (25 ml, 0.1 mol) in THF (50ml) was added dropwise over 50 minutes and while keeping the temperaturebetween 0-10° C. bromoisobutyroyl bromide (23.0 g, 0.1 mol). The mixtureis stirred for another 3 h at room temperature and the THF is thenevaporated in vacuo. Water (20 ml) is added to the residue and themixture is extracted with t-butyl-methyl ether (2×30 ml) andethylacetate (30 ml).

The combined extracts are washed with saturated NaCl solution (10 ml),dried over MgSO₄ and evaporated to afford 24.1 g of the title compoundas a colorless oil.

¹H-NMR (300 MHz, CDCl₃): 8.51 (bs, NH), 3.39-3.34 (m, CH₂), 2.47-2.43(t, CH₂), 2.25 (s, 2×CH₃), 1.94 (s, 2×CH₃), 1.72-1.64 (m, CH₂)

b)2-(2,6-Diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-1-yloxy)-N-(3-dimethylamino-propyl)-2-methyl-propionamide

2,6-diethyl-2,3,6-trimethyl-piperidine-4-hydroxy-N-oxyl (12.86 g, 0.06mol, prepared as described in DE 19909767 A1), CuCl (11.9 g, 0.12 mol),PMDETA (20.8 g, 0.12 mol) and2-bromo-N-(3-dimethylamino-propyl)-2-methyl-propionamide (16.5 g, 0.066mol) are reacted as described in Example A3 to afford 23.6 g of thetitle compound as a white amorphous solid.

¹H-NMR (300 MHz, CDCl₃): 7.4-7.25 (bs, NH), 4.19-4.11 (m, 1H), 3.44-3.24(m, 2H), 2.39-0.79 (m, 39H).

Example A11Benzyl-{3-[2-(2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-1-yloxy)-2-methyl-propionylamino]-propyl}-dimethyl-ammonium-chloride(Compound 111, Table 1)

Benzylchloride (0.87 g, 0.0069 mol) is added to a solution of2-(2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-1-yloxy)-N-(3-dimethylamino-propyl)-2-methyl-propionamide(2.2 g, 0.0057 mol, compound 110) in acetonitrile (3 ml). The mixture isstirred for 19 h at room temperature and is then evaporated. The residueis triturated with diethylether to remove the excess of benzylchloride,the solid is filtered off and dried to afford 3.0 g of the titlecompound as a colorless amorphous solid.

MS (ESI) cation C₂₈H₅₀N₃O₃ (476.4): found 476.4.

Example A12Benzyl-{3-[2-(2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-1-yloxy)-propionylamino]-propyl}-dimethyl-ammonium-chloride(Compound 112, Table 1)

Benzylchloride (3.8 g, 0.03 mol) is added to a solution of2-(2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-1-yloxy)-.N.-(3-dimethylamino-propyl)-propionamide(10.1 g, 0.0272 mol) in acetonitrile (15 ml). The mixture is stirred for18 h at room temperature and is then evaporated. The residue istriturated with diethylether to remove the excess of benzylchloride, thesolid is filtered off and dried to afford 13.1 g of the title compoundas a colorless amorphous solid.

¹H-NMR (300 MHz, MeOH-d4): 7.60-7.51 (m, C₆H₅), 4.56 (s, CH₂), 4.25-4.15(m, 2H), 3.35-3.29 (m, 4H), 3.06 (s, 6H), 2.15-0.80 (m, 29H).

Example A13Tributyl-{3-[2-(2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-1-yloxy)-propionyloxy]-propyl}-phosphonium-bromide(Compound 113, Table 1) a) 2-Bromo-propionic acid 3-bromo-propyl ester

3-Bromopropanol (10.75 g, 0.075 mol) is added over 20 minutes to asolution of 2-bromopropionylbromide (17.9 g, 0.079 mol) in toluene (75ml) while keeping the temperature between 15-20° C. The mixture isstirred for 6 h at room temperature and is then poured under vigorousstirring into 1M solution of Na₂CO₃ (80 ml). The organic layer isseparated, washed with water (3×50 ml), dried over MgSO₄ and evaporatedto afford 19.75 g of the title compound as a colorless oil.

¹H-NMR (300 MHz, CDCl₃): 4.42-4.24 (m, CH+CH₂), 3.55-3.47 (t, CH₂),2.27-2.19 (m, CH₂), 1.84-1.82 (d, CH₃).

b)2-(2,6-Diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-1-yloxy)-propionicacid 3-bromo-propyl ester

2,6-diethyl-2,3,6-trimethyl-piperidine-4-hydroxy-N-oxyl (10.7 g, 0.05mol, prepared as described in DE 19909767 A1), CuCl (9.9 g, 0.1 mol),PMDETA (17.3 g, 0.1 mol) and 2-bromo-propionic acid 3-bromo-propyl ester(17 g, 0.055 mol) are reacted as described in Example A3 to afford 16.4g of the title compound as a colorless oil.

¹H-NMR (300 MHz, CDCl₃): 4.38-4.17 (m, 4H), 3.54-3.46 (m, 2H), 2.23-0.79(m, 28H).

c) Quaternisation

Tributylphosphine (3 ml, 0.012 mol) is added to a solution of2-(2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-1-yloxy)-propionicacid 3-bromo-propyl ester (4.08 g, 0.01 mol) in acetonitrile (5 ml). Thesolution is stirred under argon at 60° C. for 23 h. The solvent isevaporated and the residue is triturated with diethyl ether (2×15 ml) toremove the excess of the phosphine. Drying of the oily, in etherinsoluble, residue affords 6.45 g of the title compound as a thickresin.

¹H-NMR (300 MHz, CDCl₃): 4.38-4.13 (m, 4H), 2.66-2.47 (m, 8H), 2.1-0.83(m, 49H).

The compounds are summarized in Table 1

TABLE 1 No Stucture 101

102

103

104

105

106

107

108

109

110

111

112

113

B) APPLICATION EXAMPLES PROOF OF POLYMERIZATION Polymerization ofn-butyl Acrylate with Cationic Alkoxyamines (NOR's)

The cationic NOR's are tested in pure n-butyl acrylate monomer: In a 50ml round bottom flask with vacuum and nitrogen inlet and magneticstirrer 10 g n-butyl acrylate (BASF, techn. quality) is mixed with 1.5mol % of the cationic alkoxyamine (NOR), evacuated and purged withnitrogen 3 times and polymerized at 140° C. (examples B1-B4) in an oilbath for 7-20 h under good stirring. The conversion is measured by¹H-NMR, M_(n) and PDI with GPC in THF, values are relative toPS-standards. The polymerization results are presented in Table 2

TABLE 2 ConversionUmsatz % M_(n) NOR Time (¹H-NMR) (found) PDI ExampleB1 17 h  90% 6980 1.47 Compound 101 Example B2 20 h  78% 5470 1.24Compound 102 Example B3 7 h 70% 6660 1.68 Compound 103 Example B4 7 h60% 5080 1.46 Compound 104 Example B5 7 h 42% 3770 1.35 Compound 106120° C. 7 H 94% 6600 1.49 140° C. Example B6 22 h  76% 4000 1.88Compound 107 140° C. Example B7 5 h 71% 6150 1.21 Compound 110 140° C.Example B8 7 h 65% 6270 1.34 Compound 111 140° C. Example B9 7 h 58%3680 2.18 Compound 112 140° C.

The results presented in Table 2 clearly show that all compounds areable to initiate a controlled polymerization of n-butylacrylate.

C) APPLICATION EXAMPLES INTERCALATION OF SHEET SILICATES WITH CATIONICNOR'S Example C1 Intercalation of Nanofil EXM 588 (Layered Silicate ofMontmorillonite-Type from Süd Chemie, Germany) with Compound 101

In a 50 ml round bottom flask 2.0 g Nanofil EXM 588 is dispersed in 30ml of a 0.05 M solution of compound 101 in water and stirred withmagnetic stirring during 24 h at R.T. After centrifugation (IEC CentraGP8 Zentrifuge, 100-180 ml glass vessels) with 2000 rpm (correspondingto ca. 850 g) during 20 min, a sample is taken of the supernatent clearsolution, from which the concentration of remaining (=non intercalated)compound 101 is determined by UV-spektroscopy at λ245 nm. Theintercalated quantity of compound 101 is determined to be 358 mg (=0.702mmol) for 1 g of layered silicate.

The supernatant solution is decanted and the solid washed with water,centrifugation and decantation 3 times. This procedure is repeated withMeOH. The sedimented, washed product is subjected to a powder X-ray(λ=1.54 Angström), giving a main reflection at 2Θ_(max.)=3.86°, whichcorresponds to an interlayer distance d of 2.29 nm. Compared with thenative sheet silicate (2Θ_(max.)=7.1°, =>d=1.24 nm) an increase of theinterlayer distance of 1.05 nm is obtained, corresponding toapproximately the size of the intercalated molecule. The reflex at2Θ_(max.)=7.1° (d=1.24 nm), corresponding to the original sheet distancehas almost completely disappeared.

In order to check the adsorbed quantity of intercalated compound 101, asample is completely dried in vacuum and the weight loss determined bythermographimetric analysis (TGA): heating rate: 10° C./min, from roomtemperature to 600° C. The obtained weight loss of 26.3% correspondsvery well to the theoretical value of 26.4%.

Examples C2-C5 are carried out in analogy to Example C1, the followingcationic NOR's are intercalated into Nanofil EXM 588: The results aregiven in Table 3.

TABLE 3 Sheet distance Example Intercalated after No. NOR amount NOR*intercalation Remarks Example Compound 22.7 wt. % 2Θ_(max.) = 4.2°, =>≈complete C2 104 (=0.47 mmol/g) d = 2.11 nm exchange Example Compound24.9 wt. % 2Θ_(max.) = 4.3°, => ≈complete C3 103 (=0.53 mmol/g) d = 2.03nm exchange Example Compound 29.2 wt. % d = 2.21 nm ≈complete C4 111(=0.61 mmol/g) exchange Example Compound   25 wt. % d = 2.10 nm≈complete C5 112 exchange *based on the total weight layered silicate +NOR compound

D) APPLICATION EXAMPLES POLYMERIZATION OF INTERCALATED SHEET SILICATESWITH CATIONIC NOR'S Example D1

In a 50 ml round bottom flask with magnetic stirring and vacuum andnitrogen inlet 0.5 g with compound 101 intercalated Nanofil EXM588 in9.5 g n-butyl acrylate (BASF, techn. quality) and 4.28 g 2-methoxypropylacetate is dispersed and homogenized in an ultrasonic bath. Afterevacuation and purging 5 times with N₂, the monomer is polymerizedduring 9 h at 140° C. (bath temperature) under vigorous stirring. Themonomer conversion, determined by ¹H-NMR, is 85%. The dispersion issubjected to centrifugation at 2000 rpm during 60 min and the sedimentedsolid washed with EtOAc and dried. 57 mg are obtained. It is shown usingTGA (see ex. 6: weight loss 250 to 600° C.: 26%, theory: 23%) that thesolid is pure intercalated Nanofil EXM 588 with compound 101 and doesnot contain polymer.

The supernatant solution is evaporated and dried. According to TGAanalysis the composition contains approximately 10% layered silicate and90% polymer.

The X-ray analysis of the solid gave only peaks at 2Θ>10°, whichindicates complete exfoliation. A sample (150 mg) of this solid isrefluxed with 15 ml 0.1 M LiBr solution in THF during 17 h at 65° C., tocleave off the polymer from the sheet silicate. After filtration molarmass (M_(n)) and PDI is determined by GPC in THF (relative toPS-standards): M_(n)=18000, M_(w)=38600, PDI=2.15.

The supernatant solution can be centrifuged during many hours (2000 rpm,corresponding to ca. 850 g), without further sedimentation. Even after10-fold dilution with EtOAC it is stable for months (no sedimentationobserved) which proves the nm size of the particles, indicating completeexfoliation.

Comparative Example D-Com

The experiment is performed in analogy to example 1 using 0.5 g withα,α′-azodiisobutyramidine-dihydrochloride intercalated Nanofil EXM588 in9.5 g n-butyl acrylate, without further solvent. Polymerization: 3 h at80° C. (bath temperature).

The dispersion is diluted with 240 ml toluene and 20 min centrifuged at2000 rpm. After washing and drying 0.35 g of a solid is obtained whichcorresponds according to TGA analysis to pure withα,α′-azodiisobutyramidine-dihydrochloride intercalated Nanofil EXM588and contains no polymer!

The supernatant solution is completely evaporated and the residuedissolved in 150 ml THF. Centrifugation 1 h with 2000 rpm gives again 50mg with α,α′-azodiisobutyramidine-dihydrochloride intercalated NanofilEXM588. After evaporation of all solvent and drying 24 h at 60° C. invacuum 2.0 g polymer with ca. 0.1 g withα,α′-azodiisobutyramidine-dihydrochloride intercalated Nanofil EXM5881is obtained in accordance with the TGA analysis: Weight loss 25° to 600°C.: 97% (calculated: 96.5%).

A sample (150 mg) of this solid is refluxed with 15 ml 0.1 M LiBrsolution in THF during 17 h at 65° C. in order to seperate the polymerfrom the sheet silicate. Afterwards the solution is filtered and M_(n)and PDI determined by GPC in THF (relative to PS-standards):M_(n)=658000, M_(w)=1360000, PDI=2.06.

The comparison of inventive example D1 with comparative example D-Comshows that the exfoliation of the layered silicate using intercalatedNOR (ex. 1) followed by controlled radical polymerization is much moreefficient: Firstly a much higher monomer conversion (85% compared to20%) is obtained; secondly only a small amount of the layered silicateis not exfoliated (11.4% compared with 80% in ex. 1), which can beexplained by an efficient initiation in all layers, and thirdly theformed polymer has a much lower, controlled molecular weight.

Example D2

In analogy to example D1, the controlled radical polymerization ofstyrene is used to exfoliate the sheet silicate Nanofil EXM588,intercalated with the cationic NOR compound 104. The exfoliated sheetsilicate contains 66 wt. % polystyrene and 34 wt. % sheet silicate asmeasured by TGA. The attached (onto the sheet silicate layers)polystyrene has a molecular weight of M_(n)=2050, M_(w)=4010 (GPCanalysis).

Example D3

In analogy to example D1, 10 g with compound 104 intercalated NanofilEXM588 (ex. 7), 40 g n-butyl acrylate (BASF, techn. quality) and 120 g2-methoxypropyl acetate is dispersed in a 350 ml round bottom flask withan ultraturax mixer during 25 min. After evacuation and purging 5 timeswith N₂, the monomer is polymerized during 18 h at 140° C. (oil bathtemperature: 155° C.) with mechanical stirring. The monomer conversion,determined by ¹H-NMR, is 33%. The dispersion is diluted with 100 ml EtOHand subjected to centrifugation at 2000 rpm during 60 min. 2 products,consisting of exfoliated sheet silicate with attached polymer areobtained:

The sedimented solid is redispersed in EtOH, centrifuged (1 h at 2000rpm) and the sedimented product dried in high vacuum at 90° C. overnight. 11.4 g of a grey solid is obtained. Weight loss measured by TGA(25° to 600° C., 10° C./min) gives 46 wt. % polymer attached to thesheet silicate (54 wt. %). In order to determine the molecular weight ofthe attached poly(n-butyl acrylate) chains, a sample (150 mg) of thissolid is refluxed with 15 ml 0.1 M LiBr solution in THF during 17 h at65° C. GPC gives a molar mass M_(n) of 3380 and M_(w)=5150,corresponding to a PDI of 1.52 and therefore the polymerization is wellcontrolled. The supernatant solution is also evaporated and dried: 18.75g solid. Weight loss measured by TGA (25° to 600° C., 10° C./min) gives60 wt. % polymer attached to the sheet silicate (40 wt. %). Thedetermination of the molecular weight of the attached poly(n-butylacrylate) chains by GPC gives a molar mass M_(n) of 2340 and M_(w)=4140,corresponding to a PDI of 1.77. Also in this fraction, thepolymerization is well controlled.

The X-ray analysis of both samples give only peaks at 2Θ>10°, indicatingcomplete exfoliation.

Example D4

In analogy to example D3, 7.5 g with compound 111 intercalated NanofilEXM588 (ex. 9), 40 g n-butyl acrylate (BASF, techn. quality) and 120 g2-methoxypropyl acetate is dispersed in a 350 ml round bottom flask withan ultraturax mixer during 25 min. After evacuation and purging 5 timeswith N₂, the monomer is polymerized during 19 h at 140° C. (oil bathtemperature: 155° C.) with mechanical stirring. The dispersion is putinto a rotavap and all the solvents are evaporated. The highly viscoussolid is than put into a Soxhlet extraction apparatus and continuouslyextracted with 300 ml EtOAc during 18 h. The remaining solid is dried inhigh vacuum at 90° C. over night: 15.5 g of a grey solid is obtained.Weight loss measured by TGA (25° to 600° C., 10° C./min) gives 64 wt. %polymer attached to the sheet silicate (36 wt. %). The determination ofthe molecular weight of the attached poly(n-butyl acrylate) chains byGPC gives a molar mass M_(n) of 2530 and M_(w)=4090, corresponding to aPDI of 1.62, indicating a well controlled polymerization.

The extracted fraction (7.1 g) contained 86 wt. % polymer and 14 wt. %sheet silicate (TGA-analysis) and a molecular weight for the attachedpoly(n-butyl acrylate) chains of M_(n) of 2470 and M_(w)=4070(PDI=1.65).

In both fractions the polymerization is well controlled and the sheetsilicate completely exfoliated (X-ray analysis).

Example D5

In analogy to example D4, 7.5 g with compound 111 intercalated NanofilEXM588 (ex. 9), 32.5 g styrene (Fluka, purum) and 75 g butylacetate(Fluka, purum) is dispersed in a 350 ml round bottom flask with anultraturax mixer during 25 min. After evacuation and purging 5 timeswith N₂, the monomer is polymerized during 24 h at 120° C. withmechanical stirring. The dispersion is precipitated in EtOH and thesolid dried in a vacuum oven at 50° C. over night: 20 g of white solid.It is grinded to a fine powder and put put into a Soxhlet extractionapparatus and continuously extracted with 300 ml EtOAc during 18 h. Theremaining solid is dried in high vacuum at 90° C. over night: 12.1 g ofa grey solid is obtained. X-ray analysis shows complete exfoliation.

Weight loss measured by TGA (25° to 600° C., 10° C./min) gives 72 wt. %polymer attached to the sheet silicate (28 wt. %). The determination ofthe molecular weight of the attached poly(n-butyl acrylate) chains byGPC gives a molar mass M_(n) of 4190 and M_(w)=4640, corresponding to aPDI of 1.11, indicating an extremely well controlled polymerization.

The extracted fraction is only 1.6 g, consisting of 82% polystyrene andonly 18% sheet silicate, as measured by TGA. This fraction mostlycontains well controlled polystyrene (M_(n)=3500, M_(w)=4230, PDI=1.21)which is not attached to the silicate layers. It is not used for testpurposes. From the overall mass balance, the styrene conversion can becalculated to be ca. 31%.

Example D6

In analogy to example D4, 5 g with compound 111 intercalated Optigel SH,25.8 g n-butyl acrylate (BASF, techn. quality) and 77.3 g2-methoxypropyl acetate (Fluka, purum) is dispersed in a 350 ml roundbottom flask with an ultraturax mixer during 25 min. After evacuationand purging 5 times with N₂, the monomer is polymerized during 19 h at140° C. with mechanical stirring. The dispersion is put into a rotavapand all the solvents are evaporated. The paste is than put into aSoxhlet extraction apparatus and continuously extracted with 300 mlEtOAc during 18 h. The remaining solid is dried in high vacuum at 90° C.over night: 6.4 g of a white solid is obtained. X-ray analysis showscomplete exfoliation. Weight loss measured by TGA (25° to 600° C., 10°C./min) gives 49 wt. % polymer attached to the sheet silicate (51 wt.%). The determination of the molecular weight of the attachedpoly(n-butyl acrylate) chains by GPC gives a molar mass M_(n) of 3270and M_(w)=5140, corresponding to a PDI of 1.57, indicating a wellcontrolled polymerization.

The extracted fraction (5.2 g) consists of almost pure polymer, notattached to sheet silicate layers. From the mass balance, the n-butylacrylate conversion can be calculated to be ca. 32%, leading to atheoretical (=calculated) molecular weight of the poly(n-butyl acrylate)chains of M_(n)=3270. This is in perfect agreement with the observedmolecular weight and corroborates again the perfect control of thepolymer chain length by this method.

1. A process for preparing a monomer/polymer clay nanocompositedispersion comprising the steps of A) providing a first aqueousdispersion of a natural or synthetic clay which can be partiallyintercalated and/or exfoliated and wherein said clay has an exchangeablecation; adding to said dispersion a compound of formula Ia, Ib, Ic, Id,Ie, II, IIIa, IIIb, IIIc, IIId, IIIe, IVa, Va, Vb, Vc, Vd or Ve andexchanging said cation at least partially and B) adding to saiddispersion at least one ethylenically unsaturated monomer andpolymerizing at least a portion of said ethylenically unsaturatedmonomer, wherein formula Ia, Ib, Ic, Id, Ie, II, IIIa, IIIb, IIIc, IIId,IIIe, IVa, Va, Vb, Vc, Vd and Ve are

wherein T₁, T₂, T₃ and T₄ are independently methyl or ethyl with theproviso that at least one is ethyl; T₅ and T₆ are hydrogen or T₅ and T₆together are a group ═O, ═NOH, ═NO—T₉ or T₅ is hydrogen and T₆ is —O—T₉or NR₉—T₉ T₉ is hydrogen, R₉ or —C(O)—R₉; T₇ is hydrogen or methyl; Q₁is a direct bond or a —CH₂— group; wherein if Q₁ is a direct bond, T₈ ishydrogen, and if Q₁ is —CH₂—, T₈ is methyl or ethyl; T₁₀ is hydrogen ormethyl; T₁₁, T₁₂, T₁₃, T₁₄, T₁₅ and T₁₆ independently are C₁-C₁₈alkyl,C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₅-C₁₂cycloalkyl, phenyl orC₇-C₉phenylalkyl; or T₁₁ is hydrogen and T₁₂ is a group —P(O)(OC₂H₅)₂and the others are as defined above; or T₁₁ and T₁₄ are a group—CH₂—O—T₉ and the others are as defined above; or T₁₆ is a group—C(O)—Y—R₅ and the others are as defined above; or T₁₁, T₁₂ and T₁₃ area group —CH₂OH; Y is O or NR₉; v is a number from 0 to 10 and w is 0 or1; K₁ and K₂ are hydrogen, C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, phenyl orC₇-C₉phenylalkyl and K₃ is a group

 where K₄ isY—[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻ or—Y—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻}_(u),where s and t are each a number from 0-4 and u is 1; or

Z is —C(O)— or a direct bond, wherein if Z is —C(O)—, K₅ has the meaningof K₄, and if Z is a direct bond, K₅ isO—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻}_(u),Q⁺X⁻, —CH₂Q⁺X⁻ or —CHCH₃Q⁺X⁻; K₇ is a group—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻{[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻}_(u),where s and t are each a number from 0-4 and u is 1; or a group —D₁—Q⁺X⁻where D₁ is C₁-C₁₂alkylene, C₁-C₁₂alkylene which is interrupted by oneor more O, S, or NR₉ atoms, C₅-C₁₂cycloalkylene or phenylene;

R₁ is C₁-C₁₈alkylene, R₂ is a direct bond or C₁-C₁₈alkylene, R₃ ishydrogen or C₁-C₁₈alkyl, R₄ is hydrogen or C₁-C₁₈alkyl, R₅, R₆ and R₇are each independently of the others hydrogen, C₁-C₁₈alkyl,C₃-C₁₂cycloalkyl, phenyl or C₇-C₉phenylalkyl or C₆-C₁₀heteroaryl, whichall may be unsubstituted or substituted by halogen, OH, NO₂, ON,C₁-C₄alkoxy, or R₅, R₆ and R₇ together with the nitrogen or phosphorousatom to which they are bonded form a 3-12 membered monocyclic orpolycyclic ring which may contain further heteroatoms; R₉ is hydrogen,C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, phenyl, C₇-C₉phenylalkyl,which all may be unsubstituted or substituted by one or more hydroxy,halogen or C₁-C₄alkoxy groups R₂₂ is C₁-C₁₈alkyl; X⁻ is the anion of aC₁-C₁₈carboxylic acid which may contain more than one carboxylic acidgroup, fluoride, chloride, bromide, iodide, nitrite, nitrate, hydroxide,acetate, hydrogen sulfate, sulfate, C₁-C₁₈alkoxy sulfate, aromatic oraliphatic sulfonate, carbonate, hydrogen carbonate, perchlorate,chlorate, tetrafluoroborate, borate, phosphate, hydrogen phosphate,dihydrogen phosphate or mixtures thereof;

where x is a number from 2 to 12; K₆ is selected from the groupconsisting of

R₃₀ is hydrogen or C₁-C₁₂alkyl; the alkyl groups are unsubstituted orsubstituted with one or more —OH, —COOH or C(O)R₃₀ groups; and the arylgroups are phenyl or naphthyl which are unsubstituted or substitutedwith C₁-C₁₂alkyl, halogen, C₁-C₁₂alkoxy, C₁-C₁₂alkylcarbonyl,glycidyloxy, OH, —COOH or —COO(C₁-C₁₂)alkyl and wherein in formula II G₁and G₂ independently represent a tertiary carbon atom to which anunsubstituted C₁-C₁₈alkyl or phenyl or with ON, COC₁-C₁₈alkyl.CO-phenyl, COOC₁-C₁₈alkyl, OC₁-C₁₈alkyl, NO₂, NHC₁—C₁₈alkyl orN(C₁-C₁₈)₂alkyl substituted alkyl or phenyl groups are bonded; or one ofG₁ and G₂ is a secondary carbon atom to which a group —P(O)(OR₂₂)₂ isbonded and the other is as defined above; or G₁ and G₂ together with thenitrogen atom to which they are bonded form a 5 to 8 memberedheterocyclic ring or a polycyclic or spirocyclic 5 to 20 memberedheterocyclic ring system which is substituted with 4 C₁-C₄alkyl groupsor C₅-C₁₂ spirocycloalkyl groups in the ortho position to the nitrogenatom and which may be further substituted with one or more C₁-C₁₈alkyl,C₁-C₁₈alkoxy or ═O groups; and which may be interrupted by a furtheroxygen or nitrogen atom; with the proviso that at least one of the 4C₁-C₄alkyl groups in ortho position to the nitrogen atom is higher alkylthan methyl; L₄ is a linking group selected from the group consisting ofa direct bond, R₁—Y or R₂—O(O)—Y— where Y is attached to G₁ and/or G₂;C₁-C₂₅alkylene, C₂-C₂₅alkylene interrupted by —O—, —S—, —SO—, —SO₂—,

 phenylene or C₅-C₈cycloalkylene; Q₂ is a direct bond, O, NR₅ or NR₅R₆;L₃ is a group containing at least one carbon atom and is such that theradical .L₃(Q⁺X⁻) derived from the group is able to initiatepolymerization of ethylenically unsaturated monomers; and the group—L₃(Q⁺X⁻) in formula II is a group


2. A process according to claim 1 wherein the aqueous phase of step A)is at least partially removed before performing step B).
 3. A processaccording to claim 1 wherein the compound is added in an amount of from1% to 100% by weight, based on the weight of the clay.
 4. A processaccording to claim 1 wherein the ethylenically unsaturated monomer oroligomer is selected from the group consisting of styrene, substitutedstyrenes, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone,vinylimidazole, maleic anhydride, (alkyl)acrylic acid anhydrides,(alkyl)acrylic acid salts, (alkyl)acrylic esters, (meth)acrylonitriles,(alkyl)acrylamides, vinyl halides, vinylidene halides and mixturesthereof.
 5. A process according to claim 4 wherein the ethylenicallyunsaturated monomers are styrene, α-methyl styrene, p-methyl styrene ora compound of formula CH₂═C(R_(a))—(C═Z)—R_(b) orCH₂C(R_(a))—(C═S)—R_(b), wherein R_(a) is hydrogen or C₁-C₄alkyl, R_(b)is NH₂, O⁻(Me⁺), glycidyl, unsubstituted C₁-C₁₈alkoxy, C₂-C₁₀₀alkoxyinterrupted by at least one N and/or O atom, or hydroxy-substitutedC₁-C₁₈alkoxy, unsubstituted C₁-C₁₈alkylamino, di(C₁-C₁₈alkyl)amino,hydroxy-substituted C₁-C₁₈alkylamino or hydroxy-substituteddi(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or —O—CH₂—CH₂—N⁺H(CH₃)₂An⁻;wherein An⁻ is an anion of a monovalent organic or inorganic acid; Me isa monovalent metal atom or the ammonium ion and.
 6. A process accordingto claim 1 wherein an acid containing unsaturated monomer is added,which is selected from the group consisting of methacrylic anhydride,maleic anhydride, itaconic anhydride, acrylic acid, methacrylic acid,itaconic acid, maleic acid, fumaric acid, acryloxypropionic acid,(meth)acryloxypropionic acid, styrene sulfonic acid,ethylmethacrylate-2-sulphonic acid, 2-acrylamido-2-methylpropane,sulphonic acid; phosphoethylmethacrylate; the corresponding salts of theacid containing monomer, and combinations thereof.
 7. A processaccording to claim 1 wherein step B) is repeated with a secondethylenically unsaturated monomer which is different from the first one,leading to a block copolymer.
 8. A process according to claim 1 whereinthe natural or synthetic clay is selected from the group consisting ofmontmorillonite, saponite, beidellite, montronite, hectorite,stevensite, vermiculite, kaolinite, hallosite, syntheticphyllosilicates, and combinations thereof.
 9. A monomer/polymer claynanocomposite dispersion obtained by a process according to claim
 1. 10.A method of improving the properties of paints, coatings, inks,adhesives, reactive diluents or thermoplastic materials which comprisesincorporating a monomer/polymer clay nanocomposite dispersion accordingto claim 9 therein.
 11. A process according to claim 1 wherein thecompound of formula Ia, Ib, Ic, Id, Ie, II, IIIa, IIIb, IIIc, IIId,IIIe, IVa, Va, Vb, Vc, Vd or Ve is a compound of formula IIa, IIb, IIc,IId or IIe

wherein A₁ and A₂ are independently hydrogen or together with the carbonatom to which they are bonded form a carbonyl group, —C(O)—; D is adirect bond or C₁-C₁₂alkylene, C₁-C₁₂alkylene which is interrupted byone or more O, S, or NR₉ atoms, C₅-C₁₂cycloalkylene or phenylene; E is agroup —NR₉—(CH₂)_(x)—NR₉— where x is a number from 2 to 12, or a group

v is a number from 0 to 10 and w is 0 or
 1. 12. A process according toclaim 1 wherein the compound of formula Ia, Ib, Ic, Id, Ie, II, IIIa,IIIb, IIIc, IIId, IIIe, IVa, Va, Vb, Vc, Vd or Ve is a compound offormula Ia1, Ib1, Ic1, Id1 or Ie1

wherein Q₁ is a direct bond or CH₂; T₁ and T₃ are ethyl and T₂ and T₄are methyl; T₇ is methyl or H; T₁₀ is H if T₇ is methyl and T₁₀ ismethyl if T₇ is H; if Q₁ is a direct bond, T₈ is H; if Q₁ is CH₂, T₈ ismethyl or ethyl; T₁₁, T₁₂, T₁₃, T₁₄, T₁₅ and T₁₆ are independentlymethyl or ethyl; or T₁₁ is H, T₁₂ is isopropyl, T₁₃ is phenyl and T₁₄,T₁₅, and T₁₆ are methyl; or T₁₁ is H, T₁₂ is —P(═O)(OC₂H₅)₂, T₁₃ ist-butyl and T₁₄, T₁₅, and T₁₆ are methyl; or T₁₁ and T₁₄ are —CH₂O—T₉and T₁₂ and T₁₅ are methyl or phenyl and T₁₃ and T₁₆ are methyl orethyl; or T₁₁, T₁₂, T₁₃, T₁₄, T₁₅ are methyl and T₁₆ is a group —CO—O—R₉or —CON(R₉)₂; or T₁₁, T₁₂ and T₁₃ are —CH₂OH, T₁₄ is H, T₁₅ is isopropyland T₁₆ phenyl; T₉ is hydrogen, R₉ or —C(O)—R₉, where R₉ is hydrogen,C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, phenyl or C₇-C₉phenylalkyl;K₁ is H, K₂ is methyl or ethyl and K₃ is a group

K₄ is —Y—CH₂—CH₂—(CH₂)_(s)—N⁺X⁻R₅R₆R₇ or;—Y—CH₂—CHOH—CH₂—N—CH₂—CH₂—(CH₂)_(s)—N⁺X⁻R₅R₆R₇ where Y is O or NR₉ and sis a number from 0 to 2; if K₃ is

 Z is —CO— or a direct bond; and if Z is —CO—, K₅ has the same meaningas K₄; if Z is a direct bond, K₅ is a group—O—CH₂—CHOH—CH₂—N—CH₂—CH₂—(CH₂)_(s)—N⁺X⁻R₅R₆R₇ or —CH₂N⁺R₅R₆R₇X⁻.
 13. Aprocess for preparing a monomer/polymer clay nanocomposite dispersioncomprising the steps of A) providing a first aqueous dispersion of anatural or synthetic clay which can be partially intercalated and/orexfoliated and wherein said clay has an exchangeable cation; adding tosaid dispersion a compound of formula VIa and exchanging said cation atleast partially and B) adding to said dispersion at least oneethylenically unsaturated monomer and polymerizing at least a portion ofsaid ethylenically unsaturated monomer, wherein formula VIa is

T₁, T₂, T₃ and T₄ are independently methyl or ethyl with the provisothat at least one is ethyl; T₇ is hydrogen or methyl;

 where x is a number from 2 to 12; R₅ and R₆ are each independently ofthe others hydrogen, C₁-C₁₈alkyl, C₃-C₁₂cycloalkyl, phenyl orC₇-C₉phenylalkyl or C₆-C₁₀heteroaryl, which all may be unsubstituted orsubstituted by halogen, OH, NO₂, ON, C₁-C₄alkoxy; X⁻ is the anion of aC₁-C₁₈carboxylic acid which may contain more than one carboxylic acidgroup, fluoride, chloride, bromide, iodide, nitrite, nitrate, hydroxide,acetate, hydrogen sulfate, sulfate, C₁-C₁₈alkoxy sulfate, aromatic oraliphatic sulfonate, carbonate, hydrogen carbonate, perchlorate,chlorate, tetrafluoroborate, borate, phosphate, hydrogen phosphate,dihydrogen phosphate or mixtures thereof; K₁ and K₂ are hydrogen,C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, phenyl or C₇-C₉phenylalkyl and K₃ is agroup —COK₄ or

 where K₄ isY—[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻ or—Y—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(S)—N⁺R₅R₆R₇X⁻}_(u),where s and t are each a number from 0-4 and u is 1; or K₄ is a group

Z is —C(O)— or a direct bond, wherein if Z is —C(O)—, K₅ has the meaningof K₄, and if Z is a direct bond, K₅ isO—CH₂—CHOH—CH₂—N⁺R₅R₆X⁻—{[(CH₂—CH₂)—(CH₂)_(s)—N⁺R₅R₆X⁻]_(t)—CH₂—CH₂—(CH₂)_(s)—N⁺R₅R₆R₇X⁻}_(u),Q⁺X⁻, —CH₂Q⁺X⁻ or CHCH₃Q⁺X⁻; and

R₇ is hydrogen, C₁-C₁₈alkyl, C₃-C₁₂cycloalkyl, phenyl orC₇-C₉phenylalkyl or C₆-C₁₀heteroaryl, which all may be unsubstituted orsubstituted by halogen, OH, NO₂, CN, C₁-C₄alkoxy, or R₅, R₆ and R₇together with the nitrogen or phosphorous atom to which they are bondedform a 3-12 membered monocyclic or polycyclic ring which may containfurther heteroatoms.
 14. A process for preparing a monomer/polymer claynanocomposite dispersion comprising the steps of A) providing a firstaqueous dispersion of a natural or synthetic clay which can be partiallyintercalated and/or exfoliated and wherein said clay has an exchangeablecation; adding to said dispersion a compound of formula IIa1, IIb1, IIc1or IId1 and exchanging said cation at least partially and B) adding tosaid dispersion at least one ethylenically unsaturated monomer andpolymerizing at least a portion of said ethylenically unsaturatedmonomer wherein formula IIa1, IIb1, IIc1 and IId1 are

wherein Q₁ is a direct bond or CH₂; T₁ and T₃ are ethyl and T₂, T₄ andT₇ are methyl; if Q₁ is a direct bond, T₈ is H; and if Q₁ is CH₂, T₈ ismethyl or ethyl; D is a direct bond, C₁-C₁₂alkylene or phenylene; E is—NR₅—(CH₂)_(x)—NR₅— where x is 2 to 12 or a group

 wherein Y is ═NR₉; K₁ is H, K₂ is methyl or ethyl and K₃ is a group

K₄ is —Y—CH₂—CH₂—(CH₂)_(s)—N⁺X⁻R₅R₆R₇ or—Y—CH₂—CHOH—CH₂—N—CH₂—CH₂—(CH₂)_(s)—N⁺X⁻R₅R₆R₇, where Y is O or NR₉ ands is a number from 0 to 2; R₉ is hydrogen, C₁-C₁₈alkyl, C₃-C₁₈alkenyl,C₃-C₁₈alkinyl, phenyl or C₇-C₉phenylalkyl; if K₃ is

 Z is —CO— or a direct bond; if Z is —CO—, K₅ has the same meaning asK₄; if Z is a direct bond, K₅ is a group—O—CH₂—CHOH—CH₂—N—CH₂—CH₂—(CH₂)_(s)—N⁺X⁻R₅R₆R₇ or —CH₂N⁺R₅R₆R₇X⁻; and X⁻is the anion of a C₁-C₁₈carboxylic acid which may contain more than onecarboxylic acid group, fluoride, chloride, bromide, iodide, nitrite,nitrate, hydroxide, acetate, hydrogen sulfate, sulfate, C₁-C₁₈alkoxysulfate, aromatic or aliphatic sulfonate, carbonate, hydrogen carbonate,perchlorate, chlorate, tetrafluoroborate, borate, phosphate, hydrogenphosphate, dihydrogen phosphate or mixtures thereof.
 15. A processaccording to claim 13 wherein the ethylenically unsaturated monomer oroligomer is selected from the group consisting of styrene, substitutedstyrenes, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone,vinylimidazole, maleic anhydride, (alkyl)acrylic acid anhydrides,(alkyl)acrylic acid salts, (alkyl)acrylic esters, (meth)acrylonitriles,(alkyl)acrylamides, vinyl halides, vinylidene halides or mixturesthereof.
 16. A process according to claim 14 wherein the ethylenicallyunsaturated monomer or oligomer is selected from the group consisting ofstyrene, substituted styrenes, conjugated dienes, acrolein, vinylacetate, vinylpyrrolidone, vinylimidazole, maleic anhydride,(alkyl)acrylic acid anhydrides, (alkyl)acrylic acid salts,(alkyl)acrylic esters, (meth)acrylonitriles, (alkyl)acrylamides, vinylhalides, vinylidene halides and mixtures thereof.
 17. A monomer/polymerclay nanocomposite dispersion obtained by a process according to claim13.
 18. A monomer/polymer clay nanocomposite dispersion obtained by aprocess according to claim 14.